Curing Agent For Low Temperature Cure Applications

ABSTRACT

The present invention provides N,N′-dimethyl secondary diamine polymers including methylamine-terminated poly-(N-methylazetidine) and methylamine-terminated poly-(N-methylazacycloheptane). Amine compositions and amine-epoxy compositions comprising N,N′-dimethyl secondary diamine polymers are also disclosed.

BACKGROUND OF THE INVENTION

The present invention relates generally to N,N′-dimethyl secondarydiamine polymeric compounds, amine and amine-epoxy compositionsemploying such compounds, and methods of making epoxy resincompositions.

Epoxy resins which are cured, hardened, or crosslinked withmultifunctional amines, i.e., amine compounds having three or moreactive amine hydrogens, are well known in the industry. These materialsare widely used in applications such as coatings, adhesives, composites,and civil engineering applications such as formulations for flooring. Incoating applications, amine-cured epoxy formulations generally can becured at room temperature to yield films with high mechanical strength,good water, chemical, and corrosion resistance, and excellent adhesionproperties, particularly to metallic substrates. Thus, they are oftenemployed as primers and topcoats for large structures such as ships,bridges, and industrial plants and equipment.

Before regulations placing limits on the volatile organic compound (VOC)content of amine-epoxy coatings, formulations were often based on solidepoxy resins. These resins are solid at room temperature. Coatings usingsolid epoxy resins usually dried very quickly, since only solventevaporation, not chemical cure, was required for the coating to reach adry-to-touch state.

Due to the VOC regulations, epoxy resins that are liquids at roomtemperature have replaced solid epoxy resins in many applications. Thistransition has resulted in several problems, for example, in coatingapplications. Amine-epoxy compositions based upon liquid epoxy resinstend to cure much more slowly than a comparable solid epoxy resinformulation, and this problem becomes more severe at lower temperatures.Shipyards, for example, often reside in locations with cold winters, andpaint must be applied when temperatures are about 5° C. or colder.Certain amine-epoxy coating formulations cure very slowly at thesetemperatures, often requiring at least 24 hours, and in some cases muchmore than 24 hours, to reach the “walk-on” dry state required so thatpainters can apply a second or third coat, if required. In thelaboratory, the “walk-on” dry state is often estimated by thethumb-twist test method. Slow drying times can dramatically impact ashipyard's productivity. Thus, fast cure speed at below room temperatureis a desirable property in many applications.

It is also beneficial to limit the volatility of the amine component inthe amine-epoxy formulation. In addition to meeting VOC regulations,reducing volatility can reduce worker exposure and safety concerns.

Amine-epoxy coating formulations based on a liquid epoxy resin, asopposed to a solid epoxy resin, can also be less flexible than requiredfor certain rigorous applications. For example, in ships employingmodern double hull construction, the steel used in the two hulls thatform the ballast tank is a thinner gauge than used in single hull ships.As a result of the thinner gauge, the steel flexes more which can leadto a stress crack failure of the coating, especially around weldedjoints. This in turn can lead to corrosion, which can be expensive torepair and can affect the ship's integrity. Further, in the rail carindustry, there are also problems due to lack of coating flexibility atthe weld seams. Additionally, coatings in many other applicationsrequire greater flexibility, for example, to achieve a desired impactresistance for a given application, or to post-form a metal afterpainting. In the end-use application, the amount of stress ordeformation that the material undergoes, as well as the rate ofdeformation, are important factors for determining the flexibilityrequired and thus the suitability of a particular amine-epoxycomposition or formulation.

Many epoxy coatings are over-coated with a second or third coating. Theadditional coatings are not limited to epoxy-based systems and caninclude other chemical coating systems (e.g., polyurethanes) in order toprovide particular end-use properties, such as corrosion resistance,weatherability, etc. Intercoat adhesion in formulations based on liquidepoxy resins typically is less than comparable solid epoxy resinformulations, often leading to intercoat adhesion failures. Whenadequate intercoat adhesion for a liquid epoxy system is obtained,re-coating often must occur within a limited time frame if intercoatadhesion failures are to be avoided. This time is often referred to asthe re-coat window.

Many amine-epoxy coatings suffer from problems referred to in theindustry as blush, carbamation, and exudate. These problems, in part,are due to the incompatibility of the amine curing agent and the epoxyresin, which causes phase separation and results in amine migration tothe coating surface. In primary amines, the migratory amine can reactwith CO₂ present in the air, resulting in carbamation. Whether in theform of carbamation or the greasy surface layer referred to as exudateor blush, these surface defects detract from the appearance of thecoating, and can lead to intercoat adhesion failures if the film isre-coated. These problems are generally worse for coatings applied andcured at colder temperatures, where amine-epoxy compatibility isreduced.

There are several broad classes of multifunctional amine curing agentsthat are employed in the amine-epoxy coating industry, includingpolyamides, phenalkamines, and amine adducts. None of these knownproducts addresses the needs or solves the problems noted above.Accordingly, it is to this end that the present invention is directed.

BRIEF SUMMARY OF THE INVENTION

The present invention discloses novel N,N′-dimethyl secondary diaminepolymers, and methods of making these new compounds. These polymers canhave a number-average molecular weight (M_(n)) from about 140 to about1000, and can be selected from a methylamine-terminated polyoxypropylenepolymer, a methylamine-terminated polyoxypropylene polyoxyethylenecopolymer, or a polymer having the following formula:

wherein X is a moiety having the formula:

wherein:

R₁ is a C₂-C₈ linear or branched alkanediyl; and

n comprises integers, the average of which is determined as a functionof M_(n).

In an aspect the invention provides a method for making an N,N′-dimethylsecondary diamine polymer having a number-average molecular weight (Mn)from about 140 to about 1000, the polymer having the following formula:

wherein X has the formula (I), as indicated above; R₁ and n are asdefined above, which comprises(i) adding one of an appropriate nitrile and monomethylamine to theother in a reactor by delayed addition mode at about 40 to 80° C. in anitrile to monomethylamine molar ratio of 0.6:1 to 2.2:1 to form anintermediate nitrile by the Michael addition reaction, and(ii) continuously adding the intermediate nitrile to a liquid phasecontaining monomethylamine in a 0.1 to 0.75 wt ratio of monomethylamineto total intermediate nitrile feed, in the presence of hydrogen at ahydrogen pressure of 1.38-20.7 MPa (200-3000 psig) a temperature from 70to 150° C. and a hydrogenation catalyst at 0.75 to 5 wt % of the totalintermediate nitrile feed.

In one aspect, the present invention provides an amine curing agentcomposition comprising:

(i) 90% to 10% by weight, based on total amine curing agent composition,of at least one N,N′-dimethyl secondary diamine polymer having anumber-average molecular weight (M_(n)) from about 140 to about 1000;and(ii) 10% to 90% by weight, based on total amine curing agentcomposition, of at least one multifunctional amine having 3 or moreactive amine hydrogens.Further, an amine-epoxy composition can comprise the contact product ofthe amine curing agent composition and an epoxy component comprising atleast one multifunctional epoxy resin.

In another aspect, the present invention is directed to an amine-epoxycomposition comprising the contact product of:

(a) an amine curing agent component comprising at least oneN,N′-dimethyl secondary diamine polymer selected from amethylamine-terminated polyoxypropylene polymer, amethylamine-terminated polyoxypropylene polyoxyethylene copolymer, or apolymer having the formula:

wherein X has the formula (I), as indicated above; R₁ and n are asdefined above; and the at least one N,N′-dimethyl secondary diamine hasa M_(n) from about 140 to about 1000; and(b) an epoxy component comprising at least one multifunctional epoxyresin.

In another aspect, the present invention is directed to an amine-epoxycomposition comprising the contact product of:

(a) an amine curing agent component comprising:

(i) 90% to 10% by weight, based on total amine curing agent component,of at least one N,N′-dimethyl secondary diamine polymer selected from amethylamine-terminated polyoxypropylene polymer, amethylamine-terminated polyoxypropylene polyoxyethylene copolymer, or apolymer having the formula:

wherein X has the formula (I), as indicated above; R₁ and n are asdefined above; and the at least one N,N′-dimethyl secondary diamine hasa M_(n) from about 140 to about 1000; and

(ii) 10% to 90% by weight, based on total amine curing agent component,of at least one multifunctional amine having 3 or more active aminehydrogens; and

(b) an epoxy component comprising at least one multifunctional epoxyresin.

In yet another aspect, an amine-epoxy composition is provided thatcomprises the contact product of an amine curing agent component and anepoxy component, the epoxy component comprising at least onemultifunctional epoxy resin. In this aspect, the amine componentcomprises 90% to 10% by weight of methylamine-terminatedpoly-(N-methylazetidine) and 10% to 90% by weight of at least onemultifunctional amine having 3 or more active amine hydrogens. Theweight percentages are based on the total amine curing agent component.

The present invention also provides a method of making an epoxy resincomposition comprising:

(a) forming an amine component comprising:

(i) 90% to 10% by weight, based on total amine component, of at leastone N,N′-dimethyl secondary diamine polymer selected from amethylamine-terminated polyoxypropylene polymer, amethylamine-terminated polyoxypropylene polyoxyethylene copolymer, or apolymer having the formula:

wherein X has the formula (I), as indicated above; R₁ and n are asdefined above; and the at least one N,N′-dimethyl secondary diamine hasa M_(n) from about 140 to about 1000; and

(ii) 10% to 90% by weight, based on total amine component, of at leastone multifunctional amine having 3 or more active amine hydrogens; and

(b) contacting the amine component with at least one multifunctionalepoxy resin at a stoichiometric ratio of epoxy groups in themultifunctional epoxy resin to amine hydrogens in the amine componentranging from about 1.5:1 to about 1:1.5.

In another aspect, the present invention provides an amine curing agentcomposition which can be used to cure, harden, or crosslink an epoxyresin. This composition can comprise:

(i) 90% to 10% by weight, based on total amine curing agent composition,of at least one N,N′-dimethyl secondary diamine polymer selected from amethylamine-terminated polyoxypropylene polymer, amethylamine-terminated polyoxypropylene polyoxyethylene copolymer, or apolymer having the formula:

wherein X has the formula (I), as indicated above; R₁ and n are asdefined above; and the at least one N,N′-dimethyl secondary diamine hasa M_(n) from about 140 to about 1000; and

(ii) 10% to 90% by weight, based on total amine curing agentcomposition, of at least one multifunctional amine having 3 or moreactive amine hydrogens.

In yet another aspect, the present invention provides for an aminecuring agent composition comprising:

(i) about 80% to about 20% by weight, based on total amine curing agentcomposition, of at least one N,N′-dimethyl secondary diamine selectedfrom methylamine-terminated poly-(N-methylazetidine),methylamine-terminated poly-(N-methylazacycloheptane), or a combinationthereof; and(ii) about 20% to about 80% by weight, based on total amine curing agentcomposition, of at least one multifunctional amine having 6 or morecarbon atoms and 3 or more active amine hydrogens.

Amine-epoxy compositions of the present invention can be used to producecoatings with improved “walk-on” dry times, rapid hardness development,good gloss and surface appearance, and/or outstanding impact resistanceand flexibility as compared to conventional amine-epoxy coatings.

DEFINITIONS

The following definitions and abbreviations are provided in order to aidthose skilled in the art in understanding the detailed description ofthe present invention.

-   -   AHEW—amine hydrogen equivalent weight.    -   A1618—Ancamine® 1618, commercially available from Air Products        and Chemicals, Inc., amine adduct derivative of a cycloaliphatic        amine, AHEW=115.    -   A2050—Ancamide® 2050, commercially available from Air Products        and Chemicals, Inc., polyamide adduct, ANEW=150.    -   A2390—Ancamine® 2390, commercially available from Air Products        and Chemicals, Inc., a flexibilized, modified cycloaliphatic        amine, ANEW=204.

A2603—Ancamine® 2603, commercially available from Air Products andChemicals, Inc., aliphatic amine adduct, AHEW=175.

-   -   A2609—Ancamine® 2609, commercially available from Air Products        and Chemicals, Inc., Mannich base derivative of an aliphatic        amine, AHEW=75.    -   A350A—Ancamide® 350A, commercially available from Air Products        and Chemicals, Inc., polyamide, AHEW=95.    -   BA—benzyl alcohol, commercially available from Fisher Scientific        UK Ltd.    -   CX-105—Sunmide® CX-105, commercially available from Air Products        and Chemicals, Inc., phenalkamine, AHEW=142.    -   DGEBA—diglycidyl ether of bisphenol-A.    -   EEW—epoxy equivalent weight.    -   IPDA—Isophorone diamine, commercially available from Degussa AG,        AHEW 43.    -   K54—Ancamine® K54, commercially available from Air Products and        Chemicals, Inc., tris-dimethylaminomethyl phenol.    -   M_(n)—number-average molecular weight.    -   MPCA—also abbreviated as MBPCAA. MPCA is a mixture of methylene        bridged poly(cyclohexyl-aromatic)amines that fits within the        class of multifunctional amines. Ancamine® 2168, commercially        available from Air Products and Chemicals, Inc., is a MPCA with        an AHEW of 57 and is the grade utilized in the examples.    -   MXDA—Meta-xylylenediamine, commercially available from        Mitsubishi Chemical Corporation, AHEW=34.    -   NC541LV—Cardolite® NC541LV, commercially available from        Cardolite Corporation, low viscosity phenalkamine, ANEW=125.    -   PACM—Amicure® PACM, commercially available from Air Products and        Chemicals, Inc., 4,4′-diaminodicyclohexylmethane, ANEW=53.    -   PHR—parts per hundred weight resin.

DETAILED DESCRIPTION OF THE INVENTION Amine and Epoxy-Amine Compositions

The present invention discloses novel N,N′-dimethyl secondary diaminepolymers, and methods of making these new polymeric compounds. Thesepolymers can have a M_(n) from about 140 to about 1000. In anotheraspect of the present invention, such polymers can have a M_(n) fromabout 160 to about 500. N,N′-dimethyl secondary diamine polymers inaccordance with the present invention are selected from amethylamine-terminated polyoxypropylene polymer, amethylamine-terminated polyoxypropylene polyoxyethylene copolymer, or apolymer having the following formula:

wherein X is a moiety having the formula:

wherein:

R₁ is a C₂-C₈ linear or branched alkanediyl; and

n comprises integers, the average of which is determined as a functionof M_(n).

Additionally, an amine-epoxy composition can comprise the contactproduct of the N,N′-dimethyl secondary diamine polymer and an epoxycomponent comprising at least one multifunctional epoxy resin.

In another aspect, the present invention provides an amine-epoxycomposition comprising the contact product of:

(a) an amine curing agent component comprising:

(i) 90% to 10% by weight, based on total amine curing agent component,of at least one N,N′-dimethyl secondary diamine polymer selected from amethylamine-terminated polyoxypropylene polymer, amethylamine-terminated polyoxypropylene polyoxyethylene copolymer, or apolymer having the formula:

wherein X is a moiety having the formula:

wherein R₁ and n are as defined previously; and the at least oneN,N′-dimethyl secondary diamine has a M_(n) from about 140 to about1000; and

(ii) 10% to 90% by weight, based on total amine curing agent component,of at least one multifunctional amine having 3 or more active aminehydrogens; and

(b) an epoxy component comprising at least one multifunctional epoxyresin.

In a further aspect, the present invention provides a method for curingthe amine-epoxy composition as indicated above. That is, the amine-epoxycomposition comprises the contact product of an amine curing agentcomponent and an epoxy component. In another aspect, the amine-epoxycomposition is cured at a temperature of less than or equal to about 23°C. In yet another aspect, the amine-epoxy composition is cured at atemperature of less than or equal to about 5° C. The compositions of thepresent invention offer improved cure rates at temperatures at or belowroom temperature, including temperatures less than or equal to about 5°C., as compared to conventional amine-epoxy compositions.

The present invention also includes articles of manufacture comprisingan amine-epoxy composition. The amine-epoxy composition comprises thecontact product of an amine curing agent component and an epoxycomponent. Such articles can include, but are not limited to, a coating,an adhesive, a construction product, a flooring product, or a compositeproduct. Additional components or additives can be used together withthe compositions of the present invention to produce articles ofmanufacture.

In yet another aspect, an amine-epoxy composition is provided thatcomprises the contact product of an amine curing agent component and anepoxy component, the epoxy component comprising at least onemultifunctional epoxy resin. In this aspect, the amine componentcomprises 90% to 10% by weight of methylamine-terminatedpoly-(N-methylazetidine) and 10% to 90% by weight of at least onemultifunctional amine having 3 or more active amine hydrogens. Theweight percentages are based on the total amine curing agent component.

An amine curing agent composition is provided in another aspect of thepresent invention. An amine curing agent composition in accordance withthe present invention can be used to cure, harden, or crosslink an epoxyresin. Such a composition can comprise:

(i) 90% to 10% by weight, based on total amine curing agent composition,of at least one N,N′-dimethyl secondary diamine polymer having anumber-average molecular weight (M_(n)) from about 140 to about 1000;and(ii) 10% to 90% by weight, based on total amine curing agentcomposition, of at least one multifunctional amine having 3 or moreactive amine hydrogens.Additionally, an amine-epoxy composition can comprise the contactproduct of the amine curing agent composition and an epoxy componentcomprising at least one multifunctional epoxy resin.

In another aspect, the present invention provides an amine curing agentcomposition which comprises:

(i) 90% to 10% by weight, based on total amine curing agent composition,of at least one N,N′-dimethyl secondary diamine polymer selected from amethylamine-terminated polyoxypropylene polymer, amethylamine-terminated polyoxypropylene polyoxyethylene copolymer, or apolymer having the formula:

wherein X is a moiety having the formula (I), as indicated above; R₁ andn are as defined previously; and the at least one N,N′-dimethylsecondary diamine has a M_(n) from about 140 to about 1000; and(ii) 10% to 90% by weight, based on total amine curing agentcomposition, of at least one multifunctional amine having 3 or moreactive amine hydrogens.

In one aspect of the present invention, the amine component or aminecomposition can comprise up to 100% of the at least one N,N′-dimethylsecondary diamine polymer. In another aspect, the at least oneN,N′-dimethyl secondary diamine polymer can be used in amounts between10% and 90% of the total amine component. This percentage is a weightpercentage based upon the weight of the total amine component. That is,the presence of additional components are not included in the weightpercent calculation. For example, as used in the practice ofmanufacturing coatings, the amine component can be provided in a diluentor solvent such as benzyl alcohol. Thus, when a percentage by weight ofan amine component or a composition of the present invention isdiscussed, the quantity will exclude the effect of any diluents or otheradditives, unless stated otherwise. As an example, if 65 parts by weightof a N,N′-dimethyl secondary diamine polymer and 35 parts by weight of amultifunctional amine are used in conjunction with 40 parts by weightbenzyl alcohol and an additive (e.g., a filler) in a given application,the weight percent of the N,N′-dimethyl secondary diamine polymer is 65%based on the weight of the total amine component. The presence ofadditional materials does not affect the determination of the percentageof the at least one N,N′-dimethyl secondary diamine polymer in relationto the total weight of the amine component.

In accordance with one aspect of the present invention, 90% to 10% byweight of the total amine curing agent component or composition is theat least one N,N′-dimethyl secondary diamine. In another aspect, about80% to about 20% by weight of the total amine curing agent component orcomposition is the at least one N,N′-dimethyl secondary diamine. In yetanother aspect, about 75% to about 25% by weight of the total aminecuring agent component or composition is the at least one N,N′-dimethylsecondary diamine.

The relative amount of the N,N′-dimethyl secondary diamine versus thatof the multifunctional amine can vary depending upon, for example, theend-use article, its desired properties, and the fabrication method andconditions used to produce the end-use article. For instance, in coatingapplications, incorporating more N,N′-dimethyl secondary diaminerelative to the amount of the multifunctional amine generally results incoatings which have greater flexibility, a broader re-coat window, andthat cure faster and/or can be cured at lower temperatures. Conversely,incorporating relatively more multifunctional amine generally results incoatings with improved chemical resistance and often higher ultimatehardness.

An amine curing agent composition in accordance with another aspect ofthe present invention comprises:

(i) about 80% to about 20% by weight, based on total amine curing agentcomposition, of at least one N,N′-dimethyl secondary diamine selectedfrom methylamine-terminated poly-(N-methylazetidine),methylamine-terminated poly-(N-methylazacycloheptane), or a combinationthereof; and(ii) about 20% to about 80% by weight, based on total amine curing agentcomposition, of at least one multifunctional amine having 6 or morecarbon atoms and 3 or more active amine hydrogens.

In a further aspect, the weight percent, based on total amine curingagent composition, of at least one N,N′-dimethyl secondary diamineselected from methylamine-terminated poly-(N-methylazetidine),methylamine-terminated poly-(N-methylazacyclo-heptane), or a combinationthereof, ranges from about 75% to about 25%.

The present invention also provides a method of making an epoxy resincomposition comprising:

(a) forming an amine component comprising:

(i) 90% to 10% by weight, based on total amine component, of at leastone N,N′-dimethyl secondary diamine polymer selected from amethylamine-terminated polyoxypropylene polymer, amethylamine-terminated polyoxypropylene polyoxyethylene copolymer, or apolymer having the formula:

wherein X has the formula (I), as indicated above; R₁ and n are asdefined above; and the at least one N,N′-dimethyl secondary diamine hasa M_(n) from about 140 to about 1000; and

(ii) 10% to 90% by weight, based on total amine component, of at leastone multifunctional amine having 3 or more active amine hydrogens; and

(b) contacting the amine component with at least one multifunctionalepoxy resin at a stoichiometric ratio of epoxy groups in themultifunctional epoxy resin to amine hydrogens in the amine componentranging from about 1.5:1 to about 1:1.5.

In accordance with the amine-epoxy compositions and methods of making anepoxy composition disclosed herein, the stoichiometric ratio of epoxygroups in the epoxy component to amine hydrogens in the amine componentranges from about 1.5:1 to about 1:1.5. In another aspect, thestoichiometric ratio ranges from about 1.3:1 to about 1:1.3.

Additionally, it can be beneficial in the compositions of the presentinvention for all of the components to be liquids at room temperature.That is, the at least one N,N′-dimethyl secondary diamine compound, theat least one multifunctional amine compound, and the at least onemultifunctional epoxy resin compound are all liquids at roomtemperature. In this disclosure, room temperature is approximately 23°C. Applicants disclose several types of ranges in the present invention.These include, but are not limited to, a range of weight percentages, arange of temperatures, a range of number of atoms, a range of molecularweights, a range of integers, and a range of stoichiometric ratios. WhenApplicants disclose or claim a range of any type, Applicants' intent isto disclose or claim individually each possible number that such a rangecould reasonably encompass, as well as any sub-ranges and combinationsof sub-ranges encompassed therein. For example, when the Applicantsdisclose or claim a chemical moiety having a certain number of carbonatoms, Applicants' intent is to disclose or claim individually everypossible number that such a range could encompass, consistent with thedisclosure herein. For example, the disclosure that “R₁” can be a C₂ toC₈ alkanediyl group, or in alternative language having from 2 to 8carbon atoms, as used herein, refers to a “R₁” group that can beselected independently from an alkanediyl group having 2, 3, 4, 5, 6, 7,or 8 carbon atoms, as well as any range between these two numbers (forexample, a C₃ to C₆ alkanediyl group), and also including anycombination of ranges between these two numbers (for example, a C₂ to C₄and C₆ to C₈ alkanediyl group).

Similarly, another representative example follows for the weight percentof the at least one N,N′-dimethyl secondary diamine, based on the weightof the total amine component. By a disclosure that about 20% to about80% by weight of the total amine curing agent component is an at leastone N,N′-dimethyl secondary diamine, for example, Applicants intend torecite that the weight percent can be selected from about 20%, about21%, about 22%, about 23%, about 24%, about 25%, about 26%, about 27%,about 28% about 29%, about 30%, about 31%, about 32%, about 33%, about34%, about 35%, about 36%, about 37%, about 38%, about 39%, about 40%,about 41%, about 42% about 43%, about 44%, about 45%, about 46%, about47%, about 48%, about 49%, about 50%, about 51%, about 52%, about 53%,about 54%, about 55%, about 56%, about 57%, about 58%, about 59%, about60%, about 61%, about 62%, about 63%, about 64%, about 65%, about 66%,about 67%, about 68%, about 69%, about 70%, about 71%, about 72%, about73%, about 74%, about 75%, about 76%, about 77%, about 78%, about 79%,or about 80%. Likewise, all other ranges disclosed herein should beinterpreted in a manner similar to these two examples.

Applicants reserve the right to proviso out or exclude any individualmembers of any such group, including any sub-ranges or combinations ofsub-ranges within the group, that can be claimed according to a range orin any similar manner, if for any reason Applicants choose to claim lessthan the full measure of the disclosure, for example, to account for areference that Applicants may be unaware of at the time of the filing ofthe application. Further, Applicants reserve the right to proviso out orexclude any individual substituents, analogs, compounds, ligands,structures, or groups thereof, or any members of a claimed group, if forany reason Applicants choose to claim less than the full measure of thedisclosure, for example, to account for a reference that Applicants maybe unaware of at the time of the filing of the application.

The term “contact product” is used herein to describe compositionswherein the components are contacted together in any order, in anymanner, and for any length of time. For example, the components can becontacted by blending or mixing. Further, contacting of any componentcan occur in the presence or absence of any other component of thecompositions or formulations described herein. Combining additionalmaterials or components can be done by any method known to one of skillin the art.

While compositions and methods are described in terms of “comprising”various components or steps, the compositions and methods can also“consist essentially of” or “consist of” the various components orsteps.

N,N′-Dimethyl Secondary Diamine

Polymeric compounds in accordance with this disclosure are described aseither N,N′-dimethyl secondary diamine polymers ormethylamine-terminated polymers, such as, for example,methylamine-terminated poly-(N-methylazetidine) ormethylamine-terminated polyoxypropylene. Applicants' use of thisnomenclature is to define that the terminus or end group on each side ofthe polymeric compound is a methylamine group. The methylamine endgroups are illustrated in the following structure:

Compositions of the present invention comprise at least oneN,N′-dimethyl secondary diamine polymer. N,N′-dimethyl secondary diaminepolymers having a M_(n) from about 140 to about 1000 are within thescope of the present invention. Further, the N,N′-dimethyl secondarydiamine polymer can have a M_(n) that is in a range from about 140 toabout 750, from about 140 to about 500, or from about 140 to about 300.In another aspect of the present invention, the N,N′-dimethyl secondarydiamine polymer has a M_(n) in the range from about 150 to about 750, orfrom about 160 to about 500. In yet another aspect, the M_(n) is in arange from about 160 to about 450, about 160 to about 400, about 160 toabout 350, or about 160 to about 300. In a different aspect, the M_(n)of the at least one N,N′-dimethyl secondary diamine polymer is in arange from about 165 to about 450, about 170 to about 400, about 175 toabout 350, or about 180 to about 300.

The M_(n) data in accordance with this disclosure, and the datapresented in Examples 1-5 that follow, were determined using a GasChromatography (GC) technique. This procedure used a Hewlett-Packard6890 Gas Chromatograph equipped with a flame ionization detector. Theinlet was operated at 275° C. with a 10:1 split ratio. The GC techniqueused an initial temperature of 50° C. with an initial hold time of 2minutes, followed by increasing the temperature at a rate of 7° C. perminute, up to a maximum temperature of 285° C. The maximum temperaturewas held for an additional 30 minutes. The column was a nominal 30 meterHP-5 (5% phenyl methyl silicone, 95% dimethyl silicone) capillary columnwith a nominal diameter of 530 μm and a nominal film thickness of 2.65μm. The initial flow rate of helium was 4.2 mL/min.

The M_(n) was determined by assuming that the mass of eluting materialwas proportional to the area percent obtained by this GC technique.Reaction by-products were not included in the M_(n) calculation, andonly polymeric species with sufficient volatility to elute under the GCconditions given above were included in the calculation. The M_(n) wasdetermined by dividing each area percent (proportional to mass) by themolecular weight of that particular polymeric species to yield therelative moles of that species. The sum of the relative moles of thepolymeric species was then divided into the total area percent of thepolymeric species to give M_(n). The total area percent excludes thearea percent of reaction by-products. Note that the calculation of M_(n)of the polymeric sample includes, for example, when the integer n informula (I) equals zero. As will be recognized by those skilled in theart, as M_(n) increases, at some point an alternative technique such asGel Permeation Chromatography (GPC) can be employed for the measurementof M_(n), due to the low volatility of the higher molecular weightspecies in the distribution. For some N,N′-dimethyl secondary diaminepolymers, this occurs when M_(n) exceeds about 400.

In another aspect of the present invention, the at least oneN,N′-dimethyl secondary diamine polymer can have an amine hydrogenequivalent weight (AHEW) from about 50 to about 500. Alternatively, theat least one N,N′-dimethyl secondary diamine has an AHEW from about 60to about 400, about 70 to about 300, or about 80 to about 200. In adifferent aspect, the AHEW of the at least one N,N′-dimethyl secondarydiamine is in a range from about 90 to about 150.

Yet, in another aspect, the N,N′-dimethyl secondary diamine can have theformula:

wherein X is a moiety selected from:

wherein:

R₁ is a C₂-C₈ linear or branched alkanediyl;

n, p, q, r, and s, independently, comprise integers, the respectiveaverage of these integers are determined as a function of M_(n).

By describing R₁ as an “alkanediyl” moiety, Applicants are specifyingthe number of carbon atoms in the R₁ moiety, along with the number ofhydrogen atoms required to conform to the rules of chemical valence forthat diyl moiety. For example, in formula (I), the fact that R₁ isbonded to two other groups is consistent with this description of analkanediyl moiety.

Unless otherwise specified, alkanediyl groups described herein areintended to include all structural isomers, linear or branched, of agiven moiety; for example, all enantiomers and all diasteriomers areincluded within this definition. As an example, unless otherwisespecified, the term propanediyl is meant to include 1,1-propanediyl,1,2-propanediyl, 1,3-propanediyl, and 2,2-propanediyl. Similarly,butanediyl is meant to include all stereo and regio diyl isomers ofbutane, for example, n-butane-1,1-diyl, n-butane-1,2-diyl,n-butane-1,3-diyl, n-butane-1,4-diyl, n-butane-2,3-diyl,2-methylpropane-1,1-diyl, 2-methylpropane-1,3-diyl, and so forth.

It is within the scope of the present invention that R₁ in the formula(I) is a C₂-C₈ linear or branched alkanediyl. In another aspect, R₁ is aC₃-C₈ linear or branched alkanediyl. In yet another aspect, R₁ is aC₃-C₆ linear or branched alkanediyl. Illustrative examples ofN,N′-dimethyl secondary diamine polymer compounds having the formula (I)include, but are not limited to, methylamine-terminatedpoly-(N-methylazetidine), methylamine-terminatedpoly-(N-methylazacycloheptane), and the like. The nomenclature formethylamine-terminated poly-(N-methylazetidine) andmethylamine-terminated poly-(N-methylazacycloheptane), for example, arebased on the nomenclature of other ring-opening polymerization reactionsand resulting polymers, such as the ring-opening polymerization ofethylene oxide to form poly-(ethylene oxide).

The N,N′-dimethyl secondary diamines of the present invention aredescribed as polymers, indicating that they comprise at least onerepeating unit. Applicants' use of the term “polymer” is meant toinclude all molecular weight polymers, including lower molecular weightpolymers or oligomers. Since there is not an industry accepted cutoff inmolecular weight between a polymer and an oligomer, Applicants haveelected to use the term polymer throughout this disclosure and intendfor the term polymer to encompass oligomers as well.

Since the compounds of the present invention are polymeric, theynecessarily include mixtures of different size molecules, with differentnumbers of repeating units. Further, for a N,N′-dimethyl secondarydiamine having the formula:

wherein X is a moiety selected from formulas (I), (II), or (III) asindicated above; the integers n, p, q, r, and s, respectively andindependently, can be zero.

For instance, the moiety having the formula (I) illustrates a repeatingunit in a N,N′-dimethyl secondary diamine polymeric compound, where theinteger “n” represents the number of repeating units in any givenmolecule. Since the N,N′-dimethyl secondary diamine is a polymer, it isrepresented by a mixture of molecules of various sizes, i.e., variousvalues of n. It is within the scope of the present invention for theinteger n to vary from 0 to 50 or more. In a different aspect, n informula (I) ranges from 0 to 40, or 0 to 30, or 0 to 20. In a furtheraspect, n ranges from 0 to 15. Yet, in another aspect, n ranges from 0to 10. In a different aspect, n ranges from 1 to 50, from 1 to 40, from1 to 30, or from 1 to 20, Further, n can range from 1 to 10 in oneaspect of the present invention. It is understood that n represents aninteger designating the number of repeating units for a single moleculewithin the polymer, where the polymer has a distribution of values of n,a distribution of molecular sizes, and a distribution of molecularweights. For any given N,N′-dimethyl secondary diamine polymercomprising a moiety having the formula (I), an average value of n can bereadily determined from the number-average molecular weight, M_(n).Determining an average value of n would not necessarily result in aninteger or a whole number, depending upon the respective molecularweight distribution.

Similarly, the moiety having the formula (II) comprises a propyl etherrepeating unit in an at least one N,N′-dimethyl secondary diaminepolymer. One of skill in the art would recognize that such polymericrepeating units can be derived in a manner similar to propylene oxidepolymerization. Thus, in one aspect of the present invention, the atleast one N,N′-dimethyl secondary diamine polymer ismethylamine-terminated polyoxypropylene. In formula (II), the integer“p” represents the number of repeating units in themethylamine-terminated polyoxypropylene. It is within the scope of thepresent invention for the integer p to vary from 0 to 50 or more.Alternatively, p in formula (II) ranges from 0 to 40, 0 to 30, or 0 to20. In a different aspect, p ranges from 0 to 10. In another aspect, pranges from 1 to 50, or 1 to 30, or 1 to 20, or 1 to 10.

The moiety having the formula (III) comprises propyl ether and ethylether repeating units in an at least one N,N′-dimethyl secondary diaminepolymer. One of ordinary skill in the art would recognize that suchpolymeric repeating units can be derived in a manner similar to ethyleneoxide and propylene oxide polymerization, where a polyethylene oxidechain has been capped with polypropylene oxide repeating units. Thus, inone aspect of the present invention, the at least one N,N′-dimethylsecondary diamine polymer is a methylamine-terminated polyoxypropylenepolyoxyethylene copolymer. In formula (III), the integers “q”, “r”, and“s” represent the number of repeating units in themethylamine-terminated polyoxypropylene polyoxyethylene copolymer. It iswithin the scope of the present invention for these integers,independently, to range from 0 to 50 or more. Further, these integerscan vary independently from 0 to 30, 0 to 20, or 0 to 10. Alternatively,the integers q, r, and s can vary independently from 1 to 40, 1 to 30,or 1 to 20, in another aspect of the present invention. In yet anotheraspect, integers q, r, and s range independently from 1 to 10.

Illustrative examples of N,N′-dimethyl secondary diamine polymercompounds in accordance with the present invention include, but are notlimited to, methylamine-terminated poly-(N-methylazetidine),methylamine-terminated polyoxypropylene, methylamine-terminatedpolyoxypropylene polyoxyethylene copolymers, methylamine-terminatedpoly-(N-methylazacycloheptane), and the like, or any combinationthereof. In a further aspect, the at least one N,N′-dimethyl secondarydiamine is methylamine-terminated poly-(N-methyl-azetidine).

In accordance with the present invention, methods of making these novelcompounds are disclosed. A method for making an N,N′-dimethyl secondarydiamine polymer having a number-average molecular weight (Mn) from about140 to about 1000, the polymer having the following formula:

wherein X has the formula (I), as indicated above; R₁ and n are asdefined above, which comprises(i) adding one of an appropriate nitrile and monomethylamine to theother in a reactor by delayed addition mode at about 40 to 80° C. in anitrile to monomethylamine molar ratio of 0.6:1 to 2.2:1 to form anintermediate nitrile by the Michael addition reaction, and(ii) continuously adding the intermediate nitrile to a liquid phasecontaining monomethylamine in a 0.1 to 0.75 wt ratio of monomethylamineto total intermediate nitrile feed, in the presence of hydrogen at ahydrogen pressure of 1.38-20.7 MPa (200-3000 psig) a temperature from 70to 150° C. and a hydrogenation catalyst at 0.75 to 5 wt % of the totalintermediate nitrile feed. The hydrogenation catalyst is selected fromPt, Pd, Rh and Ru.

In another aspect, a desirable process for making an N,N′-dimethylsecondary diamine polymer having a Mn above 350 would entail making theintermediate nitrile using the nitrile and monomethylamine in a 1.8:1 to2.1:1 molar ratio. The monomethylamine in the liquid phase would be at0.1 to 0.25 wt ratio of monomethylamine to total intermediate nitrilefeed, the hydrogenation catalyst would be from 1 to 5 wt % and thetemperature would be from 90 to 140° C.

Methylamine-terminated poly-(N-methylazetidine) with a moiety of theformula (I) has the following chemical structure:

wherein n is an integer as defined above.

Methylamine-terminated poly-(N-methylazetidine) can be synthesized in a2-step process of cyanoethylation followed by hydrogenation in amethylamine atmosphere. For example, methylamine-terminatedpoly-(N-methylazetidine) can be prepared by first combining methylamineand acrylonitrile in molar ratios ranging from about 1:1 to about 2:1 ina Michael reaction. Next, the resulting reaction product is hydrogenatedin the presence of additional methylamine over a suitable metal catalystsuch as, for example, platinum or palladium. Non-limiting examples ofthe synthesis of methylamine-terminated poly-(N-methylazetidine) inaccordance with the present invention are illustrated in Examples 2-5that follow.

Methylamine-terminated poly-(N-methylazacycloheptane) with a moiety ofthe formula (I) has the following chemical structure:

wherein n is as defined above.

Methylamine-terminated poly-(N-methylazacycloheptane) can be prepared bythe hydrogenation of adiponitrile in the presence of methylamine over asuitable metal catalyst such as, for example, platinum or palladium.Adiponitrile is also referred to in the literature as adipodinitrile, or1,4-dicyanobutane. A non-limiting example of the synthesis ofmethylamine-terminated poly-(N-methylazacycloheptane) in accordance withthe present invention is illustrated in Example 1 that follows.

Other N,N′-dimethyl secondary diamines having the formula,

wherein X is the following moiety of the formula (I),

can be prepared in a manner similar to that illustrated for thesynthesis of methylamine-terminated poly-(N-methylazacycloheptane). Theinteger n is as defined above. Based on the species selected for R₁, anappropriate dinitrile is selected. The respective dinitrile then can behydrogenated in the presence of methylamine over a suitable metalcatalyst such as, for example, platinum or palladium.

For example, one skilled in the art will recognize that an alternativemethod to prepare poly-(N-methylazetidine) is to select malononitrile asthe dinitrile. An alternative method for the preparation of theseN,N′-dimethyl secondary diamines is through selection of the appropriatemethylamino substituted nitrile, which is then hydrogenated in thepresence of methylamine over a suitable metal catalyst such as, forexample, platinum or palladium. Thus, if R₁ is n-propanediyl, then3-methylaminopropionitrile is selected; if R₁ is n-butanediyl, then4-methylaminobutyronitrile is selected; if R₁ is n-pentanediyl, then5-methylamino-valeronitrile is selected; if R₁ is n-hexanediyl, then6-methylaminohexanenitrile is selected, and so forth.

Methylamine-terminated polyoxypropylene and methylamine-terminatedpolyoxypropylene polyoxyethylene copolymers can be prepared by startingwith the corresponding secondary hydroxyl-terminated polypropylene oxideor secondary hydroxyl-terminated polyethylene oxide/polypropylene oxide,respectively. The process described in U.S. Pat. No. 3,654,370, which isincorporate herein by reference, can then be used, wherein methylamineis substituted for ammonia. A constructive example of the synthesis ofmethylamine-terminated polyoxypropylene in accordance with the presentinvention is illustrated in Constructive Example 6 that follows.

If desired, derivatives of N,N′-dimethyl secondary diamines can beemployed for the practice of this invention. Such derivatives includepolyamide derivatives, amidoamine derivatives, amine-epoxy adductderivatives, and combinations thereof. These derivatives are well-knownto those skilled in the art.

Multifunctional Amine

Compositions in accordance with the present invention can comprise atleast one multifunctional amine. Multifunctional amine, as used herein,describes compounds with amine functionality and which contain three (3)or more active amine hydrogens.

It can be beneficial to limit the volatility of the specificmultifunctional amine used in some applications where worker exposureand safety issues may arise. Thus, in one aspect of the presentinvention, the at least one multifunctional amine contains 6 or morecarbon atoms. In another aspect, the at least one multifunctional aminecontains 8 or more carbon atoms. In yet another aspect, the at least onemultifunctional amine contains 12 or more carbon atoms.

Non-limiting examples of multifunctional amines that are within thescope of the present invention include, but are not limited to, analiphatic amine, a cycloaliphatic amine, an aromatic amine, a Mannichbase derivative of an aliphatic amine, a cycloaliphatic amine, or anaromatic amine, a polyamide derivative of an aliphatic amine, acycloaliphatic amine, or an aromatic amine, an amidoamine derivative ofan aliphatic amine, a cycloaliphatic amine, or an aromatic amine, anamine adduct derivative of an aliphatic amine, a cycloaliphatic amine,or an aromatic amine, and the like, or any combination thereof.

More than one multifunctional amine can be used in the compositions ofthe present invention. For example, the at least one multifunctionalamine can comprise an aliphatic amine and a Mannich base derivative of acycloaliphatic amine. Also, the at least one multifunctional amine cancomprise one aliphatic amine and one different aliphatic amine.

Exemplary aliphatic amines include polyethylene amines(triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine andthe like), 1,6-hexanediamine, 3,3,5-trimethyl-1,6-hexanediamine,3,5,5-trimethyl-1,6-hexanediamine, 2-methyl-1,5-pentanediamine(commercially available as Dytek-A), bis-(3-aminopropyl)amine,N,N′-bis-(3-aminopropyl)-1,2-ethanediamine, aminoethylpiperazine, andthe like, or combinations thereof. Additionally, the poly(alkyleneoxide) diamines and triamines commercially available under the Jeffaminename from Huntsman Corporation, are useful in the present invention.Illustrative examples include, but are not limited to, Jeffamine® D-230,Jeffamine® D-400, Jeffamine® D-2000, Jeffamine® D-4000, Jeffamine®T-403, Jeffamine® EDR-148, Jeffamine® EDR-192, Jeffamine® C-346,Jeffamine® ED-600, Jeffamine® ED-900, Jeffamine® ED-2001, and the like,or combinations thereof.

Cycloaliphatic and aromatic amines include, but are not limited to,1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane,hydrogenated ortho-toluenediamine, hydrogenated meta-toluenediamine,metaxylylene diamine, hydrogenated metaxylylene diamine (referred tocommercially as 1,3-BAC), isophorone diamine, various isomers ornorbornane diamine, 3,3′-dimethyl-4,4′-diaminodicyclohexyl methane,4,4′-diaminodicyclohexyl methane, 2,4′-diaminodicyclohexyl methane, amixture of methylene bridged poly(cyclohexyl-aromatic)amines, and thelike, or combinations thereof. The mixture of methylene bridgedpoly(cyclohexyl-aromatic)amines is abbreviated as either MBPCAA or MPCA,and is described in U.S. Pat. No. 5,280,091, which is incorporatedherein by reference in its entirety. In one aspect of the presentinvention, the at least one multifunctional amine is a mixture ofmethylene bridged poly(cyclohexyl-aromatic)amines (MPCA).

Mannich base derivatives can be made by the reaction of the abovedescribed aliphatic amines, cycloaliphatic amines, or aromatic amineswith phenol or a substituted phenol and formaldehyde. An exemplarysubstituted phenol used to make Mannich bases with utility in thepresent invention is cardanol, which is obtained from cashew nut shellliquid. Alternatively, Mannich bases can be prepared by an exchangereaction of a multifunctional amine with a tertiary amine containing aMannich base, such as tris-dimethylaminomethylphenol (commerciallyavailable as Ancamine® K54 from Air Products and Chemicals, Inc.) orbis-dimethylaminomethylphenol. Polyamide derivatives can be prepared bythe reaction of an aliphatic amine, cycloaliphatic amine, or aromaticamine with dimer fatty acid, or mixtures of a dimer fatty acid and afatty acid. Amidoamine derivatives can be prepared by the reaction of analiphatic amine, cycloaliphatic amine, or aromatic amine with fattyacids. Amine adducts can be prepared by the reaction of an aliphaticamine, cycloaliphatic amine, or aromatic amine with an epoxy resin, forexample, with the diglycidyl ether of bisphenol-A, the diglycidyl etherof bisphenol-F, or epoxy novolac resins. The aliphatic, cycloaliphatic,and aromatic amines also can be adducted with monofunctional epoxyresins, such as phenyl glycidyl ether, cresyl glycidyl ether, butylglycidyl ether, other alkyl glycidyl ethers, and the like.

Multifunctional Epoxy Resin

Amine-epoxy compositions of the present invention comprise an epoxycomponent, the epoxy component comprising at least one multifunctionalepoxy resin. Multifunctional epoxy resin, as used herein, describescompounds containing 2 or more 1,2-epoxy groups per molecule. Epoxidecompounds of this type are described in Y. Tanaka, “Synthesis andCharacteristics of Epoxides”, in C. A. May, ed., Epoxy Resins Chemistryand Technology (Marcel Dekker, 1988), which is incorporated herein byreference.

One class of epoxy resins suitable for use in the present inventioncomprise the glycidyl ethers of polyhydric phenols, including theglycidyl ethers of dihydric phenols. Illustrative examples include, butare not limited to, the glycidyl ethers of resorcinol, hydroquinone,bis-(4-hydroxy-3,5-difluorophenyl)-methane,1,1-bis-(4-hydroxyphenyl)-ethane,2,2-bis-(4-hydroxy-3-methylphenyl)-propane,2,2-bis-(4-hydroxy-3,5-dichlorophenyl) propane,2,2-bis-(4-hydroxyphenyl)-propane (commercially known as bisphenol A),bis-(4-hydroxyphenyl)-methane (commercially known as bisphenol F, andwhich may contain varying amounts of 2-hydroxyphenyl isomers), and thelike, or any combination thereof. Additionally, advanced dihydricphenols of the following structure also are useful in the presentinvention:

where m is an integer, and R is a divalent hydrocarbon radical of adihydric phenol, such as those dihydric phenols listed above. Materialsaccording to this formula can be prepared by polymerizing mixtures of adihydric phenol and epichlorohydrin, or by advancing a mixture of adiglycidyl ether of the dihydric phenol and the dihydric phenol. Whilein any given molecule the value of m is an integer, the materials areinvariably mixtures which can be characterized by an average value of mwhich is not necessarily a whole number. Polymeric materials with anaverage value of m between 0 and about 7 can be used in one aspect ofthe present invention.

In another aspect, epoxy novolac resins, which are the glycidyl ethersof novolac resins, can be used as multifunctional epoxy resins inaccordance with the present invention. In yet another aspect, the atleast one multifunctional epoxy resin is a diglycidyl ether ofbisphenol-A (DGEBA), an advanced or higher molecular weight version ofDGEBA, a diglycidyl ether of bisphenol-F, an epoxy novolac resin, or anycombination thereof. Higher molecular weight versions or derivatives ofDGEBA are prepared by the advancement process, where excess DGEBA isreacted with bisphenol-A to yield epoxy terminated products. The epoxyequivalent weights (EEW) for such products ranges from about 450 to 3000or more. Because these products are solid at room temperature, they areoften referred to as solid epoxy resins.

DGEBA or advanced DGEBA resins are often used in coating formulationsdue to a combination of their low cost and generally high performanceproperties. Commercial grades of DGEBA having an EEW ranging from about174 to about 250, and more commonly from about 185 to about 195, arereadily available. At these low molecular weights, the epoxy resins areliquids and are often referred to as liquid epoxy resins. It isunderstood by those skilled in the art that most grades of liquid epoxyresin are slightly polymeric, since pure DGEBA has an EEW of 174. Resinswith EEW's between 250 and 450, also generally prepared by theadvancement process, are referred to as semi-solid epoxy resins becausethey are a mixture of solid and liquid at room temperature.

Depending upon the end-use application, it can be beneficial to reducethe viscosity of the compositions of the present invention by modifyingthe epoxy component. For example, the viscosity can be reduced to allowan increase in the level of pigment in a formulation or compositionwhile still permitting easy application, or to allow the use of a highermolecular weight epoxy resin. Thus, it is within the scope of thepresent invention for the epoxy component, which comprises at least onemultifunctional epoxy resin, to further comprise a monofunctionalepoxide. Examples of monoepoxides include, but are not limited to,styrene oxide, cyclohexene oxide, ethylene oxide, propylene oxide,butylene oxide, and the glycidyl ethers of phenol, cresols,tert-butylphenol, other alkyl phenols, butanol, 2-ethylhexanol, C₄ toC₁₄ alcohols, and the like.

Miscellaneous Additives

Compositions of the present invention can be used to produce variousarticles of manufacture. Depending on the requirements during themanufacturing of or for the end-use application of the article, variousadditives can be employed in the formulations and compositions to tailorspecific properties. These additives include, but are not limited to,solvents, accelerators, plasticizers, fillers, fibers such as glass orcarbon fibers, pigments, pigment dispersing agents, rheology modifiers,thixotropes, flow or leveling aids, defoamers, or any combinationthereof. It is understood that other mixtures or materials that areknown in the art can be included in the compositions or formulations andare within the scope of the present invention.

Further, compositions within the scope of the present invention can besolventless, also referred to as solvent-free or 100% solids.Alternatively, these compositions can further comprise at least onesolvent (a solvent is also referred to as a diluent). Often, a solventor mixture of solvents is chosen to give a specific evaporation rateprofile for the composition or formulation, while maintaining solubilityof the components of the formulation.

Articles

The present invention also is directed to articles of manufacturecomprising the compositions disclosed herein. For example, an articlecan comprise an amine-epoxy composition which comprises the contactproduct of an amine curing agent component and an epoxy component. Theamine curing agent component can comprise at least one N,N′-dimethylsecondary diamine and at least one multifunctional amine. The epoxycomponent can comprise at least one multifunctional epoxy resin.Optionally, various additives can be present in the compositions orformulations used to produce fabricated articles, dependent upon thedesired properties. These additives can include, but are not limited to,solvents, accelerators, plasticizers, fillers, fibers such as glass orcarbon fibers, pigments, pigment dispersing agents, rheology modifiers,thixotropes, flow or leveling aids, defoamers, or any combinationthereof.

Articles in accordance with the present invention include, but are notlimited to, a coating, an adhesive, a construction product, a flooringproduct, or a composite product. Coatings based on these amine-epoxycompositions can be solvent-free or can contain solvents or diluents asneeded for the particular application. For example, coatings with solidscontent greater than 50%, greater than 65%, greater than 75%, or greaterthan 85%, are within the scope of the present invention. Coatings cancontain various types and levels of pigments for use in paintapplications.

Numerous substrates are suitable for the application of coatings of thisinvention with proper surface preparation, as is well known to one ofordinary skill in the art. Such substrates include, but are not limitedto, concrete and various types of metals and alloys, such as steel andaluminum. For example, the low temperature cure, good surface appearancewhen applied at room temperature, and good flexibility properties of thecoatings of the present invention make them suitable for the painting orcoating of large metal objects or cementitious substrates which must bepainted and/or cured at room temperature or colder conditions, includingships, bridges, industrial plants and equipment, and floors. Coatings ofthis invention can be applied and cured at temperatures ranging fromabout −10° C. to about 50° C., or alternatively, at temperatures rangingfrom about 0° C. to about 35° C. As needed, these coatings also can beforce cured at higher temperatures, which often can improve theflexibility of the cured material.

Coatings of this invention can be applied by any number of techniquesincluding spray, brush, roller, paint mitt, and the like. In order toapply very high solids content or 100% solids coatings of thisinvention, plural component spray application equipment can be used, inwhich the amine and epoxy components are mixed in the lines leading tothe spray gun, in the spray gun itself, or by mixing the two componentstogether as they leave the spray gun. Using this technique can alleviatelimitations with regard to the pot life of the formulation, whichtypically decreases as both the amine reactivity and the solids contentincreases. Heated plural component equipment can be employed to reducethe viscosity of the components, thereby improving ease of application.

Construction and flooring applications include compositions comprisingthe amine-epoxy compositions of the present invention in combinationwith concrete or other materials commonly used in the constructionindustry. Compositions of the present invention can be used in theconstruction of epoxy-based floors, often in applications requiringbetter mechanical properties (e.g., improved tensile strength orimproved compressive strength) or better elongation than that normallyobtained from cementitious or other similar types of flooring materials.Crack injection and crack filling products also can be prepared from thecompositions disclosed herein, as well as polymer modified cements, tilegrouts, and the like. Non-limiting examples of composite products orarticles comprising amine-epoxy compositions disclosed herein includetennis rackets, skis, bike frames, airplane wings, glass fiberreinforced composites, and other molded products.

EXAMPLES

Coatings of amine-epoxy compositions were prepared and tested asfollows. Hardener mixtures or compositions, including amine compositionsin accordance with the present invention, were prepared by contactingand mixing the components given in the tables that follow. Therespective hardener mixture or composition, or the individual hardener,was then mixed with a multifunctional epoxy resin at the use levelindicated in the tables in parts per hundred weight resin (PHR). Theepoxy resin used in these examples was the diglycidyl ether ofbisphenol-A (DGEBA), grade D.E.R.™ 331 with an EEW in the range of 182to 192. This epoxy resin is commercially available from the Dow ChemicalCompany.

In Examples 7-38, clear coatings were applied to standard glass panelsto produce samples for drying time testing using a Beck-Koller dryingtime recorder and for hardness development by the Persoz pendulumhardness method. Clear coatings for drying time by the thumb twistmethod and for specular gloss testing were applied to uncoated, mattepaper charts (AG5350, Byk). Coatings were applied at about 75 μm WFT(wet film thickness) using a Bird bar applicator resulting in dry filmthicknesses ranging from approximately 60 to 70 μm. Coatings of Examples7-29 were cured either at 5° C. and 80% RH (relative humidity) or 25° C.and 60% RH using a Weiss climate chamber (type WEKK0057). Coatings ofExamples 30-38 were cured either at 10° C. and 60% RH or 23° C. and 60%RH using the Weiss climate chamber. Persoz Hardness was measured at thetimes indicated in the tables.

Clear coatings for impact resistance and mandrel bend testing wereapplied to respectively cold-rolled steel test panels, ground one side(approximate size 76 mm×152 mm) and cold-rolled steel, smooth finish(approximate size 76 mm×152 mm), using a nominal 75 WFT wire bar. Metaltest panels were obtained from Q Panel Lab Products. Films were curedaccording to the following schedules: (A) 14 days room temperature, roomtemperature being approximately 23° C.; (B) 14 days room temperaturefollowed by 2 hours at 80° C.; or (C) 60 days room temperature. Dry filmthicknesses were from about 60 to 80 μm following cure schedules A andC, and from about 50 to 55 μm following schedule B.

The mix viscosities for Examples 7-29 were determined using a RheolabMC20 apparatus (Physica) equipped with a Viscotherm VT10 water bath andMC20 temperature control unit. The equipment was set up with the TEK 150cone-plate and connected to a computer. After the apparatus wasequilibrated at 25° C., the gap between the cone (MK22) and plate wasset to approximately 50 μm. Samples were equilibrated at 25° C. for 24hours before testing. After mixing as indicated, excess product runningout of the gap was removed and the rotational viscosity of the mixedproduct was recorded at a 200 reciprocal second shear rate after 30seconds.

Shore A and Shore D data were obtained at the times indicated in thetables using approximately 5 mm thick epoxy castings. Castings werecured either at 10° C. and 60% RH or 23° C. and 60% RH using the Weissclimate chamber.

Mechanical strength properties of the amine-epoxy castings weredetermined using a dual column materials testing machine (Instron, model4206-006) equipped with a 104 kN load cell. For recording compressivestrength data of cubes of around 2×2×2 cm, the machine was equipped withcompressive plates and a Dynamic 25/50 mm GL Extensiometer and operatedat a crosshead speed of 2.5 mm/min. Tensile strength data were recordedusing wedge grips at a crosshead speed of 25 mm/min. The amine-epoxycastings were prepared at approximately 23° C. and cured for 7 daysprior to testing.

The pull-off adhesion strengths of clearcoat amine-epoxy castings fromboth dry and wet concrete slabs were recorded using a P.A.T. Pull-OffAdhesion Tester. Standard pre-cast concrete slabs (approximate size30×30×5 cm) were obtained from a local supplier and stored dry at roomtemperature. For measuring the adhesion to dry concrete, the concreteslabs were used without further preparation and were coated with about200 g/m² of the respective amine-epoxy formulation. Under wetconditions, concrete slabs were completely immersed in water for 24hours prior to applying the same amine-epoxy coating formulation atabout 200 g/m². After 7 days cure at ambient temperature, the flat endof a steel-faced, metal cylinder (approximate 20 mm diameter) was gluedto the coating surface using a fast curing two-component adhesive. Thematerial in a circumference around the metal cylinder was carefullyremoved down to the substrate, after which the adhesion/cohesionstrength and the mode of failure were recorded. In the tables, thefollowing abbreviations apply: A=cohesive failure of substrate;A/B=adhesive failure between substrate and primer; Y=cohesive failure ofadhesive; and, Y/Z=adhesive failure between adhesive and cylinder.

The mix viscosities and hardener viscosities for Examples 30-38 weredetermined at 23° C. using a Brookfield DVI+ viscometer equipped withSpindle 5. Gelation time, or gel-time, was recorded as the time aftermixing the epoxy resin and the respective hardener to reach a definedpoint of viscosity. For this, a Techne GT3 Gelation Timer, equipped withdisposal glass plungers (approximate size 22×5 mm) and operating at onecycle per minute, was used. Samples were equilibrated at 23° C. for 24hours before testing. Gelation time was recorded for an approximate 150g mixture charged to a 250-ml glass jar and maintained at a constanttemperature of 23° C.

Coating properties were measured in accordance with the standard testmethods listed in Table 1. Waterspot resistance is tested by placingdrops of water on the surface of the coating for a specified time andobserving the impact on the coating. This test is used in the industryto determine if the surface of the coating is damaged or aestheticallyimpacted by extended contact with water or moisture.

TABLE 1 Analytical test methods. Property Response Test Method DryingTime: Beck-Koller Recorder Thin film set times, ASTM D5895 phases 2 & 3(h) Drying Time: Thumb Twist Method Set-to-touch and thumb- ASTM D1640twist time (h) Specular Gloss Gloss at 20° and 60° ISO 2813, ASTM D523Persoz Pendulum Hardness Persoz hardness (s) ISO 1522, ASTM D4366 ImpactResistance - Tubular Impact Direct and reverse ISO 6272, ASTM D2794Tester impact (kg · cm) Mandrel Bend Test: Cylindrical Bend Elongation(%) ISO 1519, ASTM D1737 Mandrel Bend Test: Conical Bend Elongation (%)ISO 6860, ASTM D522 Shore A & D Hardness Shore A or Shore D ISO 868,ASTM D2240 Compressive Properties - Dual Compressive Strength ASTMC579-96 Column Materials Testing Machine (MPa) & Modulus (GPa) TensileProperties - Dual Column Tensile Strength (MPa), ASTM D638-99 MaterialsTesting Machine Modulus (GPa), and Elongation (%) Pull-Off AdhesionAdhesion (MPa) ISO 4624

Example 1 Synthesis of methylamine-terminatedpoly-(N-methylazacycloheptane)

135 g of adipodinitrile, 50 g of isopropanol, and 2.7 g of Pd/Al₂O₃catalyst were placed in a 1-liter stainless-steel batch pressure reactorequipped with a stirrer and 1-liter hydrogen ballast tank. The Pd/Al₂O₃catalyst is commercially available from the Johnson-Mathey Corporation.The reactor was sealed and subsequently purged with nitrogen andhydrogen to remove any air from the reactor. While stirring the reactorcontents, 85 g of anhydrous methylamine were added to the reactor. Thereactor was then pressurized with hydrogen to 1.72 MPa (250 psi), andheated to 120° C. These conditions were maintained until the rate ofhydrogen uptake from the ballast tank fell below 0.0034 MPa/min (0.5psi/min). When this occurred, the reactor pressure was raised to 5.86MPa (850 psi). These conditions were maintained until the rate ofhydrogen uptake from the ballast tank fell below 0.0034 MPa/min (0.5psi/min). The reactor was cooled to room temperature and depressurized,and the reaction product was filtered to remove the catalyst. Solventwas then removed by rotary evaporation. The resulting reaction productwas methylamine-terminated poly-(N-methylazacycloheptane) with anestimated amine hydrogen equivalent weight (ANEW) of about 121. TheM_(n) was determined to be approximately 184 using the GC techniquedescribed above. Methylamine-terminated poly-(N-methylazacycloheptane)has the following chemical structure:

In the tables that follow, the methylamine-terminatedpoly-(N-methylazacycloheptane) compound of Example 1 is designated asdimethyl secondary diamine 1, abbreviated DSD-1. DSD-1 was analyzedusing gas chromatography (GC) and had the following polymer distributionby area percent, with “others” representing reaction by-products whichwere not separated or identified using GC, nor used in determiningM_(n):

n = 0 47.6% n = 1 35.7% n = 2 5.8% others 10.9%

Example 2 Synthesis of methylamine-terminated poly-(N-methylazetidine)

282 g of acrylonitrile and 8.5 g of water were placed in a 1-literstainless-steel batch pressure reactor equipped with a stirrer. Thereactor was sealed and subsequently purged with nitrogen to remove anyair from the reactor. While stirring the reactor contents, 200 g ofmethylamine were added to the reactor over a time period of 5 hours.During the addition of the methylamine, the reactor temperature wasmaintained in range of 55-60° C. This temperature range was thenmaintained for 1.5 hours after the methylamine addition was complete.The reactor was cooled and the intermediate product removed.

120 g of isopropanol and 7.5 g of Pd/Al₂O₃ catalyst were placed in a1-liter stainless-steel batch pressure reactor equipped with a stirrerand 1-liter hydrogen ballast tank. The Pd/Al₂O₃ catalyst is commerciallyavailable from the Johnson-Mathey Corporation. The reactor was sealedand subsequently purged with nitrogen and hydrogen to remove any airfrom the reactor. While stirring the reactor contents, 90 g of anhydrousmethylamine were added to the reactor. The reactor was then pressurizedwith hydrogen to 5.86 MPa (850 psi), and heated to 120° C. Over a timeperiod of 5 hours, 450 g of the intermediate product described abovewere added to the reactor. Substantially constant reactor conditionswere maintained for approximately 2 more hours after the addition of theintermediate product was complete, at which time the rate of hydrogenuptake from the ballast tank fell below 0.0034 MPa/min (about 0.5psi/min). The reactor was cooled to room temperature and depressurized,and the reaction product was filtered to remove the catalyst. Thesolvent was then removed by rotary evaporation. The resulting reactionproduct was methylamine-terminated poly-(N-methylazetidine) with anestimated AHEW of about 100. The M_(n) was determined to beapproximately 198 using the GC technique described above.Methylamine-terminated poly-(N-methylazetidine) has the followingchemical structure:

In the tables that follow, the methylamine-terminatedpoly-(N-methylazetidine) compound of Example 2 is designated as dimethylsecondary diamine 2, abbreviated DSD-2. DSD-2 was analyzed using GC andhad the following polymer distribution by area percent, with “others”representing reaction by-products which were not separated or identifiedusing GC, nor used in determining M_(n):

n = 0 12.6% n = 1 26.1% n = 2 25.5% n = 3 14.7% n = 4 7.3% n = 5 3.5%Others 10.3%

Example 3 Synthesis of methylamine-terminated poly-(N-methylazetidine)

282 g of acrylonitrile and 8.5 g of water were placed in a 1-literstainless-steel batch pressure reactor equipped with a stirrer. Thereactor was sealed and subsequently purged with nitrogen to remove anyair from the reactor. While stirring the reactor contents, 87 g ofmethylamine were added to the reactor over a time period of 5 hours.During the addition of the methylamine, the reactor temperature wasmaintained in range of 55-60° C. This temperature range was thenmaintained for 1.5 hours after the methylamine addition was complete.The reactor was cooled and the intermediate product removed.

120 g of isopropanol and 7 g of Pd/Al₂O₃ catalyst were placed in a1-liter stainless-steel batch pressure reactor equipped with a stirrerand 1-liter hydrogen ballast tank. The Pd/Al₂O₃ catalyst is commerciallyavailable from the Johnson-Mathey Corporation. The reactor was sealedand subsequently purged with nitrogen and hydrogen to remove any airfrom the reactor. While stirring the reactor contents, about 160 g ofanhydrous methylamine were added to the reactor. The reactor was thenpressurized with hydrogen to 5.86 MPa (850 psi), and heated to 120° C.Over a time period of 5 hours, 350 g of the intermediate productdescribed above were added to the reactor. Substantially constantreactor conditions were maintained for approximately 2 more hours afterthe addition of the intermediate product was complete, at which time therate of hydrogen uptake from the ballast tank fell below 0.0034 MPa/min(0.5 psi/min). The reactor was cooled to room temperature anddepressurized, and the reaction product was filtered to remove thecatalyst. The solvent was then removed by rotary evaporation. Theresulting reaction product was methylamine-terminatedpoly-(N-methylazetidine) with an estimated AHEW of about 113. The M_(n)was determined to be approximately 253 using the GC technique describedabove. Methylamine-terminated poly-(N-methylazetidine) has the followingchemical structure:

In the tables that follow, the methylamine-terminatedpoly-(N-methylazetidine) compound of Example 3 is designated as dimethylsecondary diamine 3, abbreviated DSD-3. DSD-3 was analyzed using GC andhad the following polymer distribution by area percent, with “others”representing reaction by-products which were not separated or identifiedusing GC, nor used in determining M_(n):

n = 0 2.8% n = 1 16.6% n = 2 18.2% n = 3 20.7% n = 4 12.2% n = 5 9.2%Others 20.3%

Example 4 Synthesis of methylamine-terminated poly-(N-methylazetidine)

142.5 parts by weight of acrylonitrile and 3 parts of water were placedin a 1-liter stainless-steel batch pressure reactor equipped with astirrer. The reactor was sealed and subsequently purged with nitrogen toremove any air from the reactor. While stirring the reactor contents,100 parts by weight of methylamine were added to the reactor over a timeperiod of 4 hours. During the addition of the methylamine, the reactortemperature was maintained at 55° C. This temperature was thenmaintained for 1.5 hours after the methylamine addition was complete.The reactor was cooled and the intermediate product removed.

35 parts by weight of isopropanol and 1.5 parts of Pd/Al₂O₃ catalystwere placed in a 1-liter stainless-steel batch pressure reactor equippedwith a stirrer and 1-liter hydrogen ballast tank. The Pd/Al₂O₃ catalystis commercially available from the Johnson-Mathey Corporation. Thereactor was sealed and subsequently purged with nitrogen and hydrogen toremove any air from the reactor. While stirring the reactor contents, 30parts by weight of anhydrous methylamine were added to the reactor. Thereactor was then pressurized with hydrogen to 5.86 MPa (850 psi), andheated to 120° C. Over a time period of 4 hours, 100 parts by weight ofthe intermediate product described above were added to the reactor.Substantially constant reactor conditions were maintained forapproximately 2 more hours after the addition of the intermediateproduct was complete, at which time the rate of hydrogen uptake from theballast tank fell below 0.0034 MPa/min (0.5 psi/min). The reactor wascooled to room temperature and depressurized, and the reaction productwas filtered to remove the catalyst. The solvent was then removed byrotary evaporation. The resulting reaction product wasmethylamine-terminated poly-(N-methylazetidine) with an estimated AHEWof about 117. It had and acid value of 877 mg KOH/g and the Brookfieldviscosity was determined to be 17 mPa·s using spindle S62 @ 100 rpm. TheM_(n) was determined to be approximately 239 using the GC techniquedescribed above. Methylamine-terminated poly-(N-methylazetidine) has thefollowing chemical structure:

In the tables that follow, the methylamine-terminatedpoly-(N-methylazetidine) compound of Example 4 is designated as dimethylsecondary diamine 4, abbreviated DSD-4. DSD-4 was analyzed using GC andhad the following polymer distribution by area percent, with “others”representing reaction by-products which were not separated or identifiedusing GC, nor used in determining M_(n):

n = 0 7.2% n = 1 17.6% n = 2 18.2% n = 3 15.8% n = 4 11.3% n = 5 7.9% n= 6 4.7% n = 7 2.5% Others 14.8%

Example 5 Synthesis of methylamine-terminated poly-(N-methylazetidine)

273.5 parts by weight of acrylonitrile and 5.5 parts of water wereplaced in a 1-liter stainless-steel batch pressure reactor equipped witha stirrer. The reactor was sealed and subsequently purged with nitrogento remove any air from the reactor. While stirring the reactor contents,100 parts by weight of methylamine were added to the reactor over a timeperiod of 4 hours. During the addition of the methylamine, the reactortemperature was maintained at approximately 55° C. This temperature wasthen maintained for 1.5 hours after the methylamine addition wascomplete. The reactor was cooled and the intermediate product removed.

35 parts by weight of isopropanol and 1.5 parts of Pd/Al₂O₃ catalystwere placed in a 1-liter stainless-steel batch pressure reactor equippedwith a stirrer and 1-liter hydrogen ballast tank. The Pd/Al₂O₃ catalystis commercially available from the Johnson-Mathey Corporation. Thereactor was sealed and subsequently purged with nitrogen and hydrogen toremove any air from the reactor. While stirring the reactor contents, 30parts by weight of anhydrous methylamine were added to the reactor. Thereactor was then pressurized with hydrogen to 5.86 MPa (850 psi), andheated to 120° C. Over a time period of 4 hours, 100 parts by weight ofthe intermediate product described above were added to the reactor.Substantially constant reactor conditions were maintained forapproximately 2 more hours after the addition of the intermediateproduct was complete, at which time the rate of hydrogen uptake from theballast tank fell below 0.0034 MPa/min (0.5 psi/min). The reactor wascooled to room temperature and depressurized, and the reaction productwas filtered to remove the catalyst. The solvent was then removed byrotary evaporation. The resulting reaction product wasmethylamine-terminated poly-(N-methylazetidine) with an estimated AHEWof about 113. It had an acid value of 837 mg KOH/g and the Brookfieldviscosity was determined to be 21 mPa·s using spindle S62 @ 100 rpm. TheM_(r), was determined to be approximately 273 using the GC techniquedescribed above. Methylamine-terminated poly-(N-methylazetidine) has thefollowing chemical structure:

In the tables that follow, the methylamine-terminatedpoly-(N-methylazetidine) compound of Example 5 is designated as dimethylsecondary diamine 5, abbreviated DSD-5. DSD-5 was analyzed using GC andhad the following polymer distribution by area percent, with “others”representing reaction by-products which were not separated or identifiedusing GC, nor used in determining M_(n):

n = 0 3.4% n = 1 11.0% n = 2 15.8% n = 3 17.0% n = 4 12.7% n = 5 10.7% n= 6 6.7% n = 7 0.9% Others 17.8%

Constructive Example 6 Constructive Synthesis of Methylamine-TerminatedPolyoxypropylene

The synthesis reaction can be carried out in a continuous reactor suchas a stainless steel tube of about 3.175 cm inside diameter and about 69cm in length. First, place about 487 mL of a pre-reduced, pelletizednickel-copper-chromium catalyst in the reactor. The catalyst can containapproximately 75 mole percent nickel, 23 mole percent copper and 2 molepercent chromium, as described in U.S. Pat. No. 3,654,370, which isincorporated herein by reference. To the reactor contents, add hydrogenat a rate of about 160 liters per hour (measured at 0° C. and 1atmosphere pressure), methylamine at a rate of about 686 g/hr, and anapproximate 50% solution of polypropylene glycol in cyclohexane at arate of about 304 g/hr. The molecular weight of the polypropylene glycolused in this synthesis can be around 400. The reactor temperature shouldbe controlled at around 240° C., and the pressure maintained atapproximately 3000 psig.

The reactor effluent is subsequently stripped of methylamine andcyclohexane by heating to approximately 150° C. The resulting reactionproduct is a liquid comprising methylamine-terminated polyoxypropylene.The reaction product should have in excess of about 90% of thetheoretical content of amino groups, and less than 10% of the originalhydroxyl groups. Typically, above about 90% of the amine groups aresecondary amino groups resulting in the desired product,methylamine-terminated polyoxypropylene, which is a N,N′-dimethylsecondary diamine polymer. The distribution of molecular sizes and theM_(n) can then be determined using the GC technique previouslydescribed. Additional, the AHEW can be estimated for themethylamine-terminated polyoxypropylene using analytical methods thatare well known to those skilled in the art.

Comparative Examples 7-11 Coatings Made from Comparative Epoxy-HardenerCompositions

Formulations and the resulting properties of comparative examples 7-11are illustrated in Tables 2-3. As indicated in the tables, the coatingof Example 7 exhibited both slow dry speed and slow hardness developmentat room temperature, and particularly at 5° C. Example 7 used apolyamide adduct curing agent. The coating of Example 8 used analiphatic amine curing agent which was high in viscosity and thereforehad low solids at application viscosity. Also, the coating of Example 8had poor impact resistance. The coatings based on phenalkamines,Examples 9-10, had slow dry speeds at 5° C., particularly as measured bythe thumb twist method. Additionally, the coatings of Examples 9-10exhibited poor hardness development, waterspot resistance, reverseimpact and mandrel bend flexibility. The conventional low viscositypolyamide curing agent of Example 11 produced visually poor coatingswith slow dry speed at 5° C., as well as poor flexibility as measured byconical, mandrel, and impact resistance test results.

TABLE 2 Comparative examples cured at 25° C. or following cure schedulesA-C. Example 7 8 9 10 11 Comparative Hardener A2050 A2603 NC541LV CX-105A 350A Use Level (PHR) 80 90 67 76 50 Mix Viscosity (mPa · s) 6,5004,000 6,250 22,000 10,300 Coating Solids (weight %) At mix viscosity 8781 100 100 100 Diluted to 1 Pa · s ^(a) — 76 94 87 90 Thin Film Set Time(h) Phase 2/Phase 3   7.5/>12 1.7/3.0 4.6/5.8 —/— —/— Coating AppearanceSpecular Gloss 20°/60°  100/101  97/101 82/92 10/50 — Visual high glossHigh gloss glossy semi gloss greasy Persoz Hardness (s) Day 1/Day 7 25/270 235/340 165/275  90/190 —/— Impact Resistance (kg · cm)Direct/Reverse Schedule A 150/30 65/6  125/20 85/17 70/6  ScheduleB >200/60   80/10 115/45 Schedule C 110/10 70/6  Mandrel Bend (%elongat.) Schedule A 6.5 4.1 5.2 5.3 <3 Conical Bend (% elongat.)Schedule A 7.4 6.2 <2 <2 <2 ^(a) adjusted with xylene:butanol (3:1) tomatch comparable application viscosity

TABLE 3 Comparative examples cured at 5° C. Example 7 8 9 10 11 ThinFilm Set Time (h) Phase 2/Phase 3 >48/>48 6.7/15   14/20  9.7/15.2 30/34Coating Appearance Specular Gloss 20°/60° —/— 96/101 40/80 12/34 —/—Visual tacky High gloss greasy matte tacky Persoz Hardness (s) Day 2/Day7 —/85 25/200  —/115 25/75 —/25 Thumb Twist method Set-to-Touch Time(h) >28 10 22 24 >28 Dry-to-Handle Time (h) — 12 26 >28 — WaterspotResistance Day 1/Day 7 (1-5, 5 = best) —/4  5/5  1/3 2/3 2/3

Inventive Examples 12-21 and Comparative Examples 22-23 Coatings Madefrom Amine-Epoxy Compositions

Formulations and the resulting properties of inventive examples 12-21and comparative examples 22-23 are shown in Tables 4-5. Examples 12-21illustrate the properties obtained from exemplary formulations andcoatings utilizing compositions comprising N,N′-dimethyl secondarydiamines with multifunctional amines in accordance with the presentinvention. Comparative examples 22-23 illustrate coating propertiesusing multifunctional amines absent N,N′-dimethyl secondary diamines.

As indicated in the tables, Examples 12-13 utilized compositionscomprising DSD-1 (a methylamine-terminatedpoly-(N-methylazacycloheptane) polymeric compound) with amultifunctional amine, MPCA. The coatings of Examples 12-13 exhibitedvery fast dry speeds, and outstanding impact flexibility. In part, thisis exemplified by comparing the thin film set time and impact resistanceat 25° C. for Examples 12-13 with the comparable coating properties ofExamples 22-23.

Examples 14-21 utilized compositions comprising a methylamine-terminatedpoly-(N-methylazetidine) polymeric compound (DSD-2, DSD-3, or DSD-4) andat least one multifunctional amine. The coatings of Examples 14-21exhibited varying combinations of fast dry speeds, rapid hardnessdevelopment, good surface appearance, and outstanding impact resistanceand flexibility. For instance, Examples 15, 17, and 18 each provided abeneficial combination of properties for applications requiring fastthin film set time at both 25° C. and 5° C., rapid hardness developmentat 25° C., and superior impact resistances and mandrel or conical bendflexibility. As indicated in Examples 22-23, this combination ofproperties was not duplicated by the multifunctional amines alone.

TABLE 4 Examples 12-23 cured at 25° C. or following cure schedules A-C.Example 12 13 14 15 Hardener Composition DSD-1 66 DSD-1 78 DSD-2 62DSD-2 74 (Parts by Weight) MPCA 34 MPCA 22 MPCA 38 MPCA 26 BA 43 BA 43BA 43 BA 43 Use Level (PHR) with DGEBA 70 76 58 63 Mix Viscosity (mPa ·s) — — 650 420 Coating Solids (weight %) 88 87 89 88 Thin Film Set Time(h) Phase 2/Phase 3 2.8/3.5 2.8/3.5 3.1/3.5 3.4/3.9 Coating AppearanceSpecular Gloss 20°/60° 98/98 97/98 103/100 100/100 Visual high glosshigh gloss high gloss high gloss Persoz Hardness (s) Day 1/Day 7 285/295185/200 305/330 265/310 Impact Resistance (kg · cm) Direct/ReverseSchedule A >200/>200 >200/>200 75/<5 170/12  ScheduleB >200/>200 >200/>200 195/70  >200/130   Schedule C Mandrel Bend (%elongat.) Schedule A — — 5.2 11 Conical Bend (% elongat.) Schedule A — —4.8 >33 Example 16 17 18 19 Hardener Composition DSD-2 55 DSD-3 65 DSD-377 DSD-3 58 (Parts by Weight) MPCA 2 MPCA 35 MPCA 23 MPCA 2 MXDA 43 BZA43 BA 43 MXDA 40 BA 43 BA 43 Use Level (PHR) with DGEBA 41 63 71 44 MixViscosity (mPa · s) 440  850 460 500  Coating Solids (weight %) 91 88 8891 Thin Film Set Time (h) Phase 2/Phase 3 3.3/3.5 3.0/3.5 3.0/3.93.3/3.6 Coating Appearance Specular Gloss 20°/60°  1/23 101/101 100/99 10/35 Visual matte high gloss high gloss matte Persoz Hardness (s) Day1/Day 7 325/335 295/305 210/250 310/320 Impact Resistance (kg · cm)Direct/Reverse Schedule A 75/<5 >200/75    >200/>200 65/<5 Schedule B170/25  >200/>200 >200/>200 105/10  Schedule C Mandrel Bend (% elongat.)Schedule A — 8.1 29 — Conical Bend (% elongat.) Schedule A — >33 >33 —Example 20 21 22 23 Hardener Composition DSD-4 75 DSD-4 75 MXDA 100 MPCA100 (Parts by Weight) IPDA 25 PACM 25 BA 43 BA 43 BA 43 BA 43 Use Level(PHR) with DGEBA 63 69 26 42 Mix Viscosity (mPa · s) 875 14,600 CoatingSolids (weight %) 88 88 94 91 Thin Film Set Time (h) Phase 2/Phase 3 —/——/— 3.3/3.7 5.8/7.1 Coating Appearance Specular Gloss 20°/60° —/— —/—40/68 103/103 Visual glossy glossy mild high gloss carbamate PersozHardness (s) Day 1/Day 7 215/220 225/230 350/360 255/340 ImpactResistance (kg · cm) Direct/Reverse Schedule A —/— —/— 45/<5 40/<5Schedule B —/— —/— 80/40 90/60 Schedule C —/— —/— 60/<5 Mandrel Bend (%elongat.) Schedule A 5.2 4.1 — — Conical Bend (% elongat.) Schedule A6.3 <2 — —

TABLE 5 Examples 12-23 cured at 5° C. Example 12 13 14 15 Thin Film SetTime (h) Phase 2/Phase 3 10.2/12.6 10.9/14.3 8.4/11.2 8.0/10.5 CoatingAppearance Specular Gloss 20°/60° 15/55 15/55 78/91  50/74  Visual tackytacky glossy carbamate free Persoz Hardness (s) Day 2/Day 7 —/— —/—85/155 55/110 Example 16 17 18 19 Thin Film Set Time (h) Phase 2/Phase 38.5/10.2 8.5/12.4  8.0/10.7 9.0/13.6 Coating Appearance Specular Gloss20°/60° 1/15 52/86  80/91 7/30 Visual matte finish mild glossycarbamate, carbamate matte finish Persoz Hardness (s) Day 2/Day 7140/220  45/135 25/55 80/240 Example 20 21 22 23 Thin Film Set Time (h)Phase 2/Phase 3 10.4/13.2 11.4/15.6 9.2/9.8 18.1/21.4  CoatingAppearance Specular Gloss 20°/60° —/— —/— 11/40 98/100 Visual —/— —/—carbamated high gloss Persoz Hardness (s) Day 2/Day 7 15/85  15/110190/275 11/140

Examples 24-25 Coatings Made from Amine-Epoxy Compositions Wherein theAmine Component Comprises a Multifunctional Amine Derivative

Tables 6-7 list the formulations and the resulting properties ofinventive examples 24-25, at 25° C. and 5° C., respectively. Examples24-25 illustrate the properties obtained from exemplary formulations andcoatings obtained from compositions comprising N,N′-dimethyl secondarydiamines with multifunctional amine derivatives in accordance with thepresent invention. Comparative examples 10-11 in Tables 2-3 illustratecoating properties using multifunctional amine derivatives absentN,N′-dimethyl secondary diamines.

In comparison to Example 11 at 25° C., the coating of Example 24exhibited significantly improved impact resistance and flexibility(mandrel and conical bend). At 5° C., Example 24 had much faster curespeed as measured by thin film set time and the thumb twist method, aswell as faster hardness development.

In comparison to Example 10 at 25° C., the coating of Example 25exhibited significantly improved impact resistance and flexibility(mandrel and conical bend). At 5° C., Example 25 had much faster curespeed as measured by thin film set time and the thumb twist method, aswell as faster hardness development. Further, Example 25 had highergloss and improved waterspot resistance at 5° C. as compared to Example10.

TABLE 6 Inventive Examples 24-25 cured at 25° C. Example 24 25 HardenerComposition DSD-4 50 g DSD-4 50 g (Parts by Weight) A 350A 50 g CX-10550 g BA 22 g BA 22 g Use Level (PHR) 63 80 Mix Viscosity (mPa · s) 2,0503,700 Coating Solids (weight %) At mix viscosity 93 92 Diluted to 1 Pa ·s ^(a) 91 91 Coating Appearance Visual greasy surface Glossy PersozHardness (s) Day 1/Day 7 —/— 245/265 Impact Resistance (kg · cm)Direct/Reverse Schedule A 170/85  200/65  Mandrel Bend (% elongat.)Schedule A 33 33 Conical Bend (% elongat.) Schedule A >33 >33 ^(a)adjusted with xylene:butanol (3:1) to match comparable applicationviscosity

TABLE 7 Inventive Examples 24-25 cured at 5° C. Example 24 25 Thin FilmSet Time (h) Phase 2/Phase 3 15.2/17.6 6.4/11.0 Thumb Twist methodSet-to-Touch Time (h) 16  9 Dry-to-Handle Time (h) 19 10 CoatingAppearance Specular Gloss 20°/60° — 86/95  Visual tacky Glossy WaterspotResistance Day 1/Day 7 (1-5, 5 = best) 2/2 4/4  Persoz Hardness (s) Day2/Day 7  —/130 95/210

Examples 26-29 Impact of the Stoichiometric Ratio of Epoxy Groups toAmine Hydrogens on Coating Properties

Table 8 lists the formulations and the resulting properties of inventiveexamples 26-29. Examples 26-29 illustrate the effect of changing thestoichiometric ratio of epoxy groups in the epoxy component to aminehydrogens in the amine component. The amine component consisted of amixture of 75 parts by weight of DSD-2, 25 parts MPCA, and 43 partsbenzyl alcohol. As indicated in Table 8, increasing the ratio of epoxygroups relative to amine hydrogens increased the dry time as measured bythin film set time, but yielded increased hardness and improvedappearance as measured by gloss.

TABLE 8 Inventive Examples 26-29. Example 26 27 28 29 StoichiometryEpoxy:Amine Groups 1:0.7 1:0.8 1:0.9 1:1.0 Use Level (PHR) 44 50 56 62Thin Film Set Time at 5° C. (h) Phase 2 9.9 8.9 8.0 8.0 AppearanceSpecular Gloss 20°/60° at 5° C. 60/85  50/73  45/65  38/60  PersozHardness (s) Day 1/Day 7 at 5° C. 40/185 55/185 50/175 50/125 Day 1 at25° C. 320 290 275 205

Comparative Examples 30-34 Coatings Made from Comparative Epoxy-HardenerCompositions

Formulations and the resulting properties of comparative examples 30-34are illustrated in Tables 9-10. As indicated in the tables, the coatingof Example 30 exhibited fast dry speed but demonstrated poor appearanceat 10° C. The coating was relatively brittle as illustrated by themechanical properties and high early hardness values. In addition,coatings based on Example 30 showed good adhesion strength to dry andwet concrete. The coatings of Examples 31-32 exhibited slow dry speedsand slow hardness development at both 23° C. and at 10° C. Example 31used IPDA, a multifunctional amine. Example 32 used an amine adductderivative of a cycloaliphatic amine. The introduction of K54 in Example33, as compared to Example 32, accelerated the dry speed and hardnessdevelopment at 10° C. and 23° C. and improved the appearance at 10° C.Coatings based on Examples 31-33 showed comparable mechanical propertiesto Example 30. The coating of Example 34 exhibited good flexibility asshown by tensile test results, but provided poor Shore hardnessdevelopment and required a very high curing agent loading (use level inPHR).

TABLE 9 Comparative examples 30-34 cured at 23° C. Example 30 31 32 3334 Comparative Hardener A2609 IPDA 57 A1618 A1618 95 A2390 (Parts byWeight) BA 43 K54 5 Use Level (PHR) 40 40 60 60 105 Hardener Viscosity(mPa · s) 450 50 520 515 1,200 Mix Viscosity (mPa · s) 1,750 2,300 2,2501,900 Gel-time (min) 14 42 50 40 18 Thin Film Set Time (h) Phase 2/Phase3 1.5/2.0 5.6/7.2 4.9/6.0 4.0/4.9 —/4.0 Coating Appearance Visual highgloss high gloss high gloss high gloss high gloss Persoz Hardness (s)  8h 140 35 30 85 — 16 h — 230 215 215 — 24 h 310 265 250 265 — Shore A/DHardness  8 h >80D 50A 40A 43D too soft 16 h — 75D 71D 77D too soft 24 h— 77D 74D 78D too soft Mechanical Compressive Compressive Strength (MPa)120 96 80 90 — Compressive Modulus (GPa) 2.2 2.1 1.6 2.0 — MechanicalTensile Tensile Strength (MPa) 46 — 51 — 22 Tensile Modulus (GPa) 7.6 —6.1 — 0.8 Elongation at Break (%) 0.7 — 0.8 — 54 Dry Concrete AdhesionPull-Off Adhesion (MPa) 10.7 — — 10.4 — Mode of Failure 100% A — — 100%A — Wet Concrete Adhesion Pull-Off Adhesion (MPa) 4.2 — — 6.5 — Mode ofFailure  50% A — — 100% A — 50% A/B

TABLE 10 Comparative examples 30-34 cured at 10° C. Example 30 31 32 3334 Thin Film Set Time (h) Phase 2/Phase 3 3.5/4.1 14.3/19.0 11.5/15.710.2/13.0 —/— Coating Appearance Visual carbamated semi gloss semi glosshigh gloss — Persoz Hardness (s)  8 h — 20 20 25 — 16 h — 45 35 60 — 24h — 120  105  140  — Shore A/D Hardness  8 h — 30A 20A 60A — 16 h — 70A65A 55D — 24 h — 65D 60D 68D —

Inventive Examples 35-38 Coatings Made from Amine-Epoxy Compositions

Formulations and the resulting properties of inventive examples 35-38are shown in Tables 11-12. Examples 35-38 illustrate the propertiesobtained from exemplary formulations and coatings utilizing compositionscomprising N,N′-dimethyl secondary diamines with multifunctional aminesin accordance with the present invention.

As indicated in the tables, Examples 35-38 utilized compositionscomprising DSD-4 (a methylamine-terminated poly-(N-methylazetidine)polymeric compound) with at least one multifunctional amine, either IPDAor A1618. Since A1618 as supplied includes benzyl alcohol, the benzylalcohol content in the curing agent in Examples 36-38 was substantiallyequal to that of Examples 31-33. In comparison to Example 31-32, thecoatings of Examples 35-37 exhibited faster drying speeds and more rapidhardness development at both 23° C. and 10° C. Additionally, coatingsbased on Example 35 provided longer gel time and lower neat curing agentviscosity, and hence lower anticipated mix viscosity than Example 30.Furthermore, coatings based on Example 35 provided better pull-offadhesion strength to concrete, particularly to wet concrete.

In comparison to Example 34, the coating based on Example 38 exhibitedsignificantly higher flexibility as illustrated by tensile elongation atbreak while offering lower curing agent viscosity for better producthandling. In comparison to Examples 32-33, Example 38 exhibitedsignificantly faster drying speeds at both 23° C. and 10° C. In part,this is exemplified by comparing the thin film set time at bothtemperatures and the gel-time at 23° C. In addition, when compared toExample 30, the coating based on Example 38 provided higher pull-offadhesion strength to concrete, particularly to wet concrete.

TABLE 11 Inventive examples 35-38 cured at 23° C. Example 35 36 37 38Hardener Composition DSD-4 30 DSD-4 18 DSD-4 37 DSD-4 37 (Parts byWeight) IPDA 34 IPDA 38 IPDA 20 A1618 35 BA 36 BA 43 BA 43 BA 28 UseLevel (PHR) 50 50 68 86 Hardener Viscosity (mPa · s) 46 49 48 80 MixViscosity (mPa · s) Gel-time (min) 27 31 21 20 Thin Film Set Time (h)Phase 2/Phase 3 3.7/4.6 4.3/5.6 3.4/4.4 2.9/4.4 Coating AppearanceVisual glossy Glossy glossy glossy Persoz Hardness (s)  8 h 145 95 80 6016 h 300 285 215 125 24 h 300 295 230 130 Shore A/D Hardness  8 h 52D42D 32D 68A 16 h 80D 79D 75D 67D 24 h 80D 79D 77D 68D MechanicalCompressive Compressive Strength (MPa) 84 87 25 4 Compressive Modulus(GPa) 1.7 1.8 0.4 <0.1 Mechanical Tensile Tensile Strength (MPa) 16Tensile Modulus (GPa) 0.8 Elongation at Break (%) 80 Dry ConcreteAdhesion Pull-Off Adhesion (MPa) 11.5 10.6 Mode of Failure 100% A 100% AWet Concrete Adhesion Pull-Off Adhesion (MPa) 6.7 5.7 Mode of Failure100% A 100% A

TABLE 12 Inventive examples 35-38 cured at 10 C. Example 35 36 37 38Thin Film Set Time (h) Phase 2/Phase 3 8.9/11.8 10.7/13.8 8.5/11.57.9/9.2 Coating Appearance Visual semi gloss semi gloss semi gloss semigloss Persoz Hardness (s)  8 h  50 40 30 20 16 h 105 90 70 30 24 h 210200  115  75 Shore A/D Hardness  8 h 75A 75A 55A 45A 16 h 67D 65D 55D85A 24 h 78D 75D 75D 58D

1-16. (canceled)
 17. N,N′-dimethyl secondary diamine polymer having anumber-average molecular weight (M_(n)) from about 160 to about 500 andselected from a methylamine-terminated polyoxypropylene polymer, amethylamine-terminated polyoxypropylene polyoxyethylene copolymer, or apolymer having the formula:

wherein X is a moiety having the formula:

wherein: R₁ is a C₂-C₈ linear or branched alkanediyl; and n comprisesintegers, the average of which is determined as a function of M_(n). 18.An amine-epoxy composition comprising the contact product of theN,N′-dimethyl secondary diamine polymer as claimed in claim 17 and anepoxy component comprising at least one multifunctional epoxy resin. 19.An amine curing agent composition comprising: (i) 90% to 10% by weight,based on total amine curing agent composition, of at least oneN,N′-dimethyl secondary diamine polymer selected from amethylamine-terminated polyoxypropylene polymer, amethylamine-terminated polyoxypropylene polyoxyethylene copolymer, or apolymer having the formula:

wherein X is a moiety having the formula:

wherein: R₁ is a C₂-C₈ linear or branched alkanediyl; the at least oneN,N′-dimethyl secondary diamine has a number-average molecular weight(M_(n)) from about 140 to about 1000; n comprises integers, the averageof which is determined as a function of M_(n); and (ii) 10% to 90% byweight, based on total amine curing agent composition, of at least onemultifunctional amine having 3 or more active amine hydrogens.
 20. Anamine curing agent composition comprising: (i) 90% to 10% by weight,based on total amine curing agent composition, of at least oneN,N′-dimethyl secondary diamine polymer having a number-averagemolecular weight (M_(n)) from about 140 to about 1000; and (ii) 10% to90% by weight, based on total amine curing agent composition, of atleast one multifunctional amine having 3 or more active amine hydrogens.21. An amine curing agent composition comprising: (i) about 80% to about20% by weight, based on total amine curing agent composition, of atleast one N,N′-dimethyl secondary diamine selected frommethylamine-terminated poly-(N-methylazetidine), methylamine-terminatedpoly-(N-methylazacycloheptane), or a combination thereof; and (ii) about20% to about 80% by weight, based on total amine curing agentcomposition, of at least one multifunctional amine having 6 or morecarbon atoms and 3 or more active amine hydrogens.
 22. A methodcomprising curing the amine-epoxy composition of claim
 18. 23. A methodcomprising curing the amine-epoxy composition of claim 19 at atemperature of less than or equal to about 23° C.
 24. A methodcomprising curing the amine-epoxy composition of claim 20 at atemperature of less than or equal to about 5° C.
 25. A method of makingan epoxy resin composition comprising: (a) forming an amine componentcomprising: (i) 90% to 10% by weight, based on total amine component, ofat least one N,N′-dimethyl secondary diamine polymer selected from amethylamine-terminated polyoxypropylene polymer, amethylamine-terminated polyoxypropylene polyoxyethylene copolymer, or apolymer having the formula:

wherein X is a moiety having the formula:

wherein: R₁ is a C₂-C₈ linear or branched alkanediyl; the at least oneN,N′-dimethyl secondary diamine has a number-average molecular weight(M_(n)) from about 140 to about 1000; n comprises integers, the averageof which is determined as a function of M_(n); and (ii) 10% to 90% byweight, based on total amine component, of at least one multifunctionalamine having 3 or more active amine hydrogens; and (b) contacting theamine component with at least one multifunctional epoxy resin at astoichiometric ratio of epoxy groups in the multifunctional epoxy resinto amine hydrogens in the amine component ranging from about 1.5:1 toabout 1:1.5.
 26. An article of manufacture comprising the composition ofclaim
 18. 27. The article of claim 26, wherein the article is a coating,an adhesive, a construction product, a flooring product, or a compositeproduct.
 28. The article of claim 26, wherein the article is a coatingwhich is applied to a metal or cementitious substrate.
 29. A method formaking an N,N′-dimethyl secondary diamine polymer having anumber-average molecular weight (M_(n)) from about 140 to about 1000which comprises adding one of an appropriate nitrile and monomethylamineto the other in a reactor by delayed addition mode at about 40 to 80° C.in a nitrile to monomethylamine molar ratio of 0.6:1 to 2.2:1 to form anintermediate nitrile by the Michael addition reaction, and continuouslyadding the intermediate nitrile to a liquid phase containingmonomethylamine in a 0.1 to 0.75 wt ratio of monomethylamine to totalintermediate nitrile feed, in the presence of hydrogen at a hydrogenpressure of 1.38-20.7 MPa (200-3000 psig) a temperature from 70 to 150°C. and a hydrogenation catalyst at 0.75 to 5 wt % of the totalintermediate nitrile feed.
 30. The method of claim 29 for makingmethylamine-terminated poly-(N-methyl-azetidine) wherein the nitrile isacrylonitrile.
 31. The method of claim 29 for makingmethylamine-terminated poly-(N-methyl-azacycloheptane) wherein thenitrile is adipodinitrile.
 32. The N,N′-dimethyl secondary diaminepolymer of claim 17 made by adding one of an appropriate nitrile andmonomethylamine to the other in a reactor by delayed addition mode atabout 40 to 80° C. in a nitrile to monomethylamine molar ratio of 0.6:1to 2.2:1 to form an intermediate nitrile by the Michael additionreaction, and continuously adding the intermediate nitrile to a liquidphase containing monomethylamine in a 0.1 to 0.75 wt ratio ofmonomethylamine to total intermediate nitrile feed, in the presence ofhydrogen at a hydrogen pressure of 1.38-20.7 MPa (200-3000 psig) atemperature from 70 to 150° C. and a hydrogenation catalyst at 0.75 to 5wt % of the total intermediate nitrile feed.
 33. The diamine polymer ofclaim 32 wherein the N,N′-dimethyl secondary diamine polymer ismethylamine-terminated poly-(N-methyl-azetidine) and the nitrile isacrylonitrile.
 34. The diamine polymer of claim 32 wherein theN,N′-dimethyl secondary diamine polymer is methylamine-terminatedpoly-(N-methyl-azacycloheptane) and the nitrile is adipodinitrile.